JPH03228060A - Photosensitive resin composition - Google Patents

Abstract

PURPOSE:To provide a photosensitive resin composition superior in water developability and storage stability by mixing cross-linkable resin particles nonchangeable in the particle form by water development and swelling and the like nd having dimensional stability. CONSTITUTION:The photosensitive resin composition comprises (I) the cross- linkable resin particles prepared by emulsion polymerizing a mixture of a resin (i) having a glass transition point Tg of <=0 deg.C, another resi (ii) having a Tg by 20 deg.C higher than that of the resin (i),or a monomer for forming it, a polyfunctional vinyl compound (iii), and a polymerization initiator (iv); and (II) a photopolymerizable unsaturated monomer; and (III) a photopolymerization initiator. The resin (i) is embodied by a vinyl-modified conjugated diene type silicone rubber, and the resin (ii) is embodied, preferably, by an acrylic resin, an epoxy resin, a polyamide resin, and the like, thus permitting the component (I) to impart rubber elaticity, the component (II) to enhance redispersibility into water, and the component (III) to ensure the dimensional stability of the resin particles and water developability.

Description

DETAILED DESCRIPTION OF THE INVENTION [Second Industrial Fields of Application] The present invention relates to a photosensitive resin composition widely used in newspaper printing, general commercial printing, photorenost, etc. In particular, the present invention relates to a photosensitive resin composition that has excellent water developability, storage stability, etc. and is useful in the production of printing plates such as flexo printing plates and bullet wiring boards.

"Prior Art" In recent years, so-called "water-developable" photosensitive compositions have been desired for the sake of health and operational safety, as photosensitive compositions used in the production of printing plate materials.

The present inventors have published Japanese Patent Application Laid-open No. 622385 as such.
No. 98 proposed a photosensitive resin composition containing radical copolymer crosslinked resin particles obtained by emulsion polymerization. That is, by blending crosslinked resin particles into the composition, the water dispersibility of the composition becomes the same as above, and it becomes possible to improve the water developability during the production of printing plate materials. Furthermore,
The resulting printing resin plate has improved water resistance and is suitable for use with water-based inks.

The present inventors have further developed the invention disclosed in JP-A No. 62-238598, and have developed an excellent crosslinked resin with the aim of further improving the water developability and storage stability of photosensitive resin compositions. Particles were investigated.

By the way, an excellent method for producing a wide variety of crosslinked resin particles is the so-called "post-emulsification method", which consists of dispersing raw resin components in water, making the inside of the dispersed resin particles three-dimensional, and then removing the aqueous medium. J (Japanese Patent Publication No. 60-1567
No. 17 etc.) are known.

However, when crosslinked resin particles are obtained by a subsequent emulsification method, the surfaces of the particles remain in a state where they are easily plastically deformed, so during the process of removing the aqueous medium from the umulsion, interparticle fusion is strongly activated, resulting in coarse particles. There was a problem that agglomerates were likely to form, and at that time, the aqueous medium was likely to be included inside the particle agglomerates.

This defective phenomenon significantly reduces the efficiency of the subsequent particle mass cleaning and drying process.

This phenomenon is particularly observed when the resin component is a plastic resin or elastomer with a relatively low glass transition temperature (Tg), such as Uras F-mer such as acrylic rubber, polybutanene, polyisoprene, chloroprene, polyε-caprolactone, and polytetramethylene glycol. In some cases, crosslinked resin particles produced from these materials by the post-emulsification method have extremely poor redispersibility in an aqueous medium and have not been put to practical use.

Therefore, in Japanese Patent Application No. 1-178459, the present inventors have proposed a post-emulsification method in which a resin component having a higher Tg or a monomer component for producing the same is blended with the above-mentioned resin component or elastomer component having a low Tg. If you attach it to
It has been shown that the above-mentioned problem of interparticle fusion can be solved.

1. Problems to be Solved by the Invention] The present invention provides, in addition to the excellent anti-fusing properties of the crosslinked resin particles described in the above-mentioned Japanese Patent Application No. 1178459, the excellent water developability and the excellent property that the particle shape does not change due to swelling, etc. It is an object of the present invention to provide a photosensitive resin composition containing crosslinked resin particles having excellent shape retention properties, thereby exhibiting excellent water developability and storage stability.

Means for Solving the Problems] That is, the present invention provides (1) (i) a resin with a glass transition temperature (Tg) of 0°C or less, (ii) a resin with a Tg higher than resin (i) by 20°C or more, or (n) Photopolymerizable unsaturated A photosensitive resin composition containing a monomer and (III) a photopolymerization initiator is provided.

In the production of the crosslinked resin particles (1) of the present invention, the base resin is one that exhibits remarkable interparticle fusion properties when crosslinked alone by a post-emulsification method, that is, its glass transition temperature (Tg
) is 0°C or less and is a resin or elastomer that has a polymerizable double bond (hereinafter referred to as "component (
i). ). The specific snout includes, for example, conjugated diene resins (e.g., polyitadiene, polyisoprene, polychloroprene, butyl rubber, styrene-butadiene rubber,
Acrylonitrile-butadiene rubber, styrene-isoprene-styrene block copolymer, styrene-butadiene-styrene bronoccopolymer, etc.), polyε-caprolactone, polyoxybrobylene), poly(oxytetramethylene) glycol, poly(oxypropylene) (oxytetramethylene) glycol and vinyl-modified resins of silicone rubber.

These resins or elastomers can be made hydrophilic through appropriate modification, for example, by maleating the elastomer, further neutralizing it with an amine, or modifying it with an appropriate monomer having a hydrophilic group to make it hydrophilic. It is preferable to use it by applying it and dispersing it in an aqueous medium. The number average molecular weight of the base resin is usually about 500 to 1,000,00
A range of 0 is preferable.

In component (11), there are various resins whose Tg is 20'C or more higher than that of the base resin, but among them,
Polystyrene (Tg = ] OO'C), polymethyl methacrylate (Tg = 1 () 5°C), polyethyl methacrylate (Tg - 65°C), polyisopropyl methacrylate (Tg = 81°C), poly n-butyl methacrylate (Tg = 20°C), polyacrylonitrile (Tg-1
acrylic resins (including copolymer resins) such as
Epoxy/resin (Tg=50-150°C), phoriamite resin (Tg=100-150°C), etc. are preferably used.

Also, when polymerized, T is 20°C higher than the base resin.
Examples of monomers that can provide a resin showing g include α,β-ethylenically unsaturated monomers, such as (meth)acrylic acid, and its esters (such as methyl (meth)acrylate, ethyl (meth)acrylate, isoflovir (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, glycidyl (meth)acrylate, etc.)
, its basic nitrogen atom-containing compounds (e.g. acrylamide, N, N/methylaminoethyl (meth)acrylate, N.

N-dimethylaminofurovir (meth)acrylamide,
N,N-dimethylamino/ethyl-N-(meth)acryloyl carbamate, N,N-diethylaminoethoxyethyl (meth)acrylate, etc.), acrylonitrile,
Examples include styrene monomers, vinyl acetate, vinyl chloride, and the like.

However, the above are only examples of resins and monomers that can be used, and are monomers that provide a resin with a Tg higher than the base resin by 20'C or more, or a resin with a Tg higher than the base resin by 20°C or higher when polymerized. Any part of the body can be used conveniently.

Furthermore, in the production of the crosslinked resin particles (1) of the present invention, a polyfunctional vinyl compound (hereinafter referred to as "component (iii) J") is added to the aqueous medium as a third blending component.

As such, for example, in the presence of a polymerization initiator, especially a radical polymerization initiator, the above (1) and (1)
1) It is not particularly limited as long as it can undergo crosslinking polymerization with the component. By adding such a polyfunctional vinyl compound, it is possible to obtain rigid resin particles with a higher degree of crosslinking than conventional resin particles. Therefore, when this crosslinked resin particle is used in a photosensitive resin composition, it is possible to prevent the particles from swelling due to monomers, solvents, etc., and exhibits excellent shape retention. Furthermore, since no swelling occurs, the particles can be easily removed with water or the like during the production of printing plates, resulting in excellent water developability. Specifically, component (iii) includes ethylene glycol di(meth)acrylate, neobentyl glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, brobylene glycol di(meth)acrylate, 1゜6 - Polyhydric (meth)acrylate compounds such as diol di(meth)acrylate, divinylbenzene, trivinylbenzene, and the like.

Polymerization initiator (iv) used in crosslinking polymerization reaction of resin particles
As such, a thermal polymerization initiator is preferable. As such, commonly used ones may be used, such as abbisisobutyronitrile (AIBN), oil-soluble initiators such as peroxides, 4,4'-azobis-4-/anovalerinoquacinode ( Examples include water-soluble initiators such as amine neutralized salts of ACVA).

In producing the crosslinked resin particles (1) of the present invention, the above (
After dispersing components 1) to (iv) in an aqueous medium, a crosslinking polymerization reaction is performed. The reaction composition ratio when carrying out the crosslinking polymerization reaction is component (1)/component (ii)/component (iii) -60 to 100 parts of the total weight of components (i) to (iii) above.
9910.9 to 3010.1 to 10 parts by weight, and
The amount of the polymerization initiator (1v) is preferably 0.1 to 2 parts by weight. If component (i) is less than 60 parts by weight, the processability and rubber elasticity of the resulting crosslinked resin particles will be poor, and if it exceeds 99 parts by weight, water developability will not be obtained, which is not preferred. component (n) is 0.9
If it is less than 30 parts by weight, the resulting crosslinked resin particles will have poor water developability, and if it exceeds 30 parts by weight, processability and rubber elasticity will be poor, which is not preferable. Moreover, if component (II[) is less than 0.1 part by weight, the shape retention and developability of the crosslinked resin particles will be poor;
If it exceeds 0 parts by weight, the hardness becomes too high and the workability and rubber elasticity are poor, which is not preferable.

The aqueous medium used as a dispersion medium is preferably water or a mixture of water and a hydrophilic organic solvent.

Specific examples of the hydrophilic organic solvent include lower alcohols (eg, methyl alcohol, ethyl alcohol, propyl alcohol, etc.), ethers (tetrahydrofuran, diethyl ether, butyl cellosolve, methyl cellosolve, etc.), and the like.

The amount of these hydrophilic organic solvents to be mixed with water is not particularly limited, as long as the amount makes the mixed solution a uniform solution.

As other additives, emulsifiers, or oligomers or polymers that can serve as emulsifiers may be added for purposes such as adjusting water dispersibility. Furthermore, a solvent or the like may be added for purposes such as viscosity adjustment.

There are no particular limitations on the method of adding the components (1) to (iv) above to the aqueous medium and the method of dispersing them. For example, if the initiator (1v) is oil-soluble, this and the above (1) to (iii)
) A homogeneous mixture of the components may be added while being dispersed in an aqueous medium using mechanical force such as a homogenizer, and a crosslinking polymerization reaction may be carried out during or after the addition. Or (1
) ~ (river) The crosslinking polymerization reaction may be carried out while adding another emulsion liquid in which the initiator (11) is previously dispersed in an aqueous medium to the emul/kun liquid in which the components are dispersed in an aqueous medium. . Moreover, when the initiator (iv) is water-soluble, (1)
The crosslinking polymerization reaction may be carried out while adding an aqueous solution in which the initiator (1v) is dissolved in water in advance to an emulsion liquid in which the components to (iii) are dispersed in an aqueous medium.

The above crosslinking polymerization reaction conditions are 40-100℃ 1O3-10
time is preferable.

After the crosslinking polymerization, isolation of the obtained crosslinked resin particles (1),
Perform dehydration, drying, washing, etc. These methods may be performed using conventional methods. That is, there is no problem even if the reaction mixture after the polymerization reaction is directly used to obtain dry particles by a known drying method such as spray drying or freeze drying. As an advantageous method, an inorganic salt such as calcium chloride, sodium chloride, or magnonium chloride is added to the reaction mixture, and after salting out, dry particles are obtained by filtration, washing with water, and drying (such as vacuum drying). It's okay.

Photopolymerizable unsaturated monomer (II
) may be a commonly used one, for example one having an ethylenically unsaturated group, preferably one having a polyfunctional ethylenically unsaturated group in order to impart higher water resistance to the cured resin plate after exposure. be. Specific examples of the monomer (n) include unsaturated carbonic acids (e.g. (meth)acrylic acid, maleic acid, itaconic acid), unsaturated carboxylic acid esters (e.g. n-butyl (meth)acrylate, 2-
Ethylhexyl(meth)acrylate, lauryl(meth)acrylate, stearyl(meth)acrylate, polyethylene glycol mono(meth)acrylate, methoxypolyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, phenoxypolyethylene glycol mono(meth)acrylate meth)acrylate, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, diaryl itaconate, glycerol meth)acrylate,
Glycerol (1) acrylate, 1,3-propylene glycol/(meth)acrylate, 1,4-cyclohedoxan/ol/(meth)acrylate, 1. ．．
2.4-butanetrioltri(meth)acrylate,
Glycerol polypropylene glycol tri(meth)acrylate, 1,4-benzenediol di(meth)acrylate, pentaerythritol tetra(meth)acrylate, tetramethylene glycol di(meth)acrylate), 1,5-pentanediol di(meth)acrylate acrylate, 1,6-hexanethiol di(meth)acrylate, unsaturated amides (e.g. methylene bis(meth)acrylamide, ethylene bis(meth)acrylamide, 1,
6-hexamethylene bis(meth)acrylamide, diethylenetriamine tris(meth)acrylamide, N-
(hydroxymethyl)acrylamide, N-(hydroxymethyl)methacrylamide, N-(β-hydroxyethyl)acrylamide, N-(β-hydroxyethyl)
Methacrylamide, N,N'-bis(β-hydroxyethyl)acrylamide, N,N'-bis(β-hydroxy/ethyl)methacrylamide, divinyl esters (e.g. divinyl adipate, divinyl phthalate), acrylated or methacrylated Urethanes (derived from hydroquinoalkyl acrylates or hydroquinoalkyl methacrylates and iso/anate compounds), diacrylic or dimethacrylic esters, or noeboxy/polyethers derived from aromatic compounds and polyalcohols, such as bisphenols or novolak compounds. etc. One or more of these compounds may be used, with water-insoluble monomers generally being preferred.

Among the monomers (It) mentioned above, those having an acidic group or a basic group are formed into salts in advance in order to improve water developability during the production of resin plates, and this is used to form a salt in the resin composition of the present invention. It may be mixed with. That is, for example, when a monomer or an acidic group is to be removed, it can be partially or completely neutralized with a basic nitrogen-triple compound (for example, the one mentioned above for component (11)). may be used to form a salt, which may be incorporated into the composition. Alternatively, if the monomer has a basic group, it can be partially or completely neutralized with an acidic compound (e.g. (meth)acrylic acid, maleic acid, itaconic acid, etc.) to form a salt. may be added to the composition.

The photopolymerization initiator (III) used in the present invention may be one commonly used, such as benzene ethers (e.g. EVA, benzoin isobutyl ether, benzoin isobutyl ether), benzophenones (e.g. EVA, benzophenone, methyl- penzoylhenzoate), xanthones (e.g. bovine santhone, thioxanthone, 2-chlorothixanthone), acetophenones (e.g. acetophenone, trichloroacetophenone, 2,2-diethoxy/acetophenone, 2,2-diphthoquine-2-phenylacetophenone) ), benzyl, 2-ethylanthraquinone, methylbenzoylformate, 2-hydroki/-
Examples include 2-methylpropiophenone, 2-methylpropiophenone, 2-methyl-4-isopropylisofropiophenone, and 1-hydroquinone chlorohexyl-phenylketone. These may be used alone or in combination.

In the composition of the composition of the present invention, the above (1) to (III)
) 532 minutes, component (I) /
Component (II)/'Component (III)-30-9015-7
010°01 to 10 parts by weight is preferred. Ingredient (1) or 3
If it is less than 0 parts by weight, the water developability and water resistance of the cured resin plate will be poor, and if it is more than 90 parts by weight, sufficient hardness cannot be imparted to the cured resin plate. If component (II) is less than 5 parts by weight, the composition will not be sufficiently photocured, and if it exceeds 70 parts by weight, the solid retention property of the resin plate will be poor. If the component (I[[) is less than 0.01 parts by weight, sufficient photosensitivity cannot be imparted to the photosensitive resin plate, and if it exceeds 10 parts by weight, the image quality on the cured resin printing plate will be poor, which is not preferable.

In addition to the above-mentioned components, the photosensitive resin composition of the present invention may contain surfactants (e.g., polyethylene di-11 alcohol/nylphenyl ether, etc.), antioxidants (e.g., 2,6-di-t, etc.), and additives. -, butyl-p-cresol, etc.), polymerization inhibitors to suppress polymerization during storage (e.g.,
(eg, hydrocarbon nonmonomethyl ether, etc.), and a solvent for adjusting viscosity (eg, glycerin, sorbitan esters, etc.) may be added.

The photosensitive resin composition of the present invention may be prepared by a conventional method, for example, by uniformly mixing the components (1) to (III) above using a kneader or the like.

A printing plate material can be produced using the photosensitive resin composition of the present invention obtained as described above. That is, the obtained photosensitive resin composition was spread to a constant thickness on a support base (for example, a metal plate coated with primer) using a hot roll coater, and then exposed and cured by applying a negative film. Thereafter, by washing and removing the unexposed areas using a water developing device, a relief image can be obtained faithfully to the negative film.

[Effects of the invention] Component (1) imparts rubber elasticity to the crosslinked resin particles used in the present invention, and component (II) solves the problem of fusion between resin particles, thereby improving redispersibility in water. improved,
Furthermore, component (III) ensures the shape retention and water developability of the resin particles.

The above-mentioned crosslinked resin particles are produced by a post-emulsification method. Therefore, while the usual emulsion polymerization method is limited to the production of vinyl resins (e.g., diene resins) from radically polymerizable monomers, various resins, such as rubber elastomers, can also be used as raw materials for crosslinked resins. Can adapt. Further, in the emulsion polymerization method, only monomers are generally used as crosslinking raw materials, but these monomers, such as butadiene, are volatile substances with low boiling points, and have problems in terms of manufacturing process and safety. However, in the post-emulsification method,
Since a resin can be used as a crosslinking raw material, handling of volatile substances can be avoided and the above problem can be solved.

In the photosensitive resin composition of the present invention, by using the crosslinked resin particles having the above-mentioned excellent processing properties, the water dispersibility of the composition is further improved and excellent water developability is imparted. or,
Since the particle form of the crosslinked resin particles is maintained in the composition for a long time, the storage stability of the photosensitive resin composition is excellent.

Furthermore, the relief plate produced using the photosensitive resin composition of the present invention has excellent elasticity, transparency, strength, and durability.
It also has appropriate hardness and water resistance. Therefore, when used as a printing plate, it has excellent resistance not only to oil-based inks but also to water-based inks. Furthermore, it provides a cured image that is sufficiently applicable to printed wiring boards.

"Examples" Hereinafter, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited by these Examples.

(Preparation of component (1)) Reference Example 1 In a 2 g capacity four-loop flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, LIR-300 (polybutadiene, estimated molecular weight 145,000, manufactured by Kuraray) was placed. 500 parts of xylene solution <solid content aV 90%), 30 parts of maleic anhydride and N0CRAC6C (N-phenyl-(1
, 3-dimethylbutyl) p-phenyl/amine (manufactured by Ohmukai Shinko Kagaku Kogyo) was charged, and then a reaction was carried out at 190° C. for 6 hours under a nitrogen stream.

To the obtained maleated polybutanene were further added 58 parts of 2-hydroquine methacrylate 26L Emulken 109P (polyethylene oxide monolauryl ether, manufactured by Kao), 1 part of hydroquinone, 3 parts of N,N-dimethylbenzylamine and 330 parts of xylene. 135℃1
The reaction was carried out for 30 minutes.

The obtained resin had a solid concentration of 60% and an average molecular weight of 56.40.
0 and resin solid content acid value of 38, and it was confirmed by IR spectrum measurement that it had a double bond capable of radical polymerization.

Reference Example 2 A xylene solution of LIR-30 (polyisoprene, estimated molecular weight 29,000, manufactured by Kuraray) (solid content a degree 90%) 500 parts, maleic anhydride 3
0 parts and N0CRAC6C(N-phenyl-(1,3-
(dimethylbutyl)-p phenyldiamine (manufactured by Ohmukai Shinko Kagaku Kogyo) was charged, and then 1 part was heated under a nitrogen stream.
The reaction was carried out at 90°C for 6 hours.

To the obtained maleated polyisoprene, 26 parts of 2-hydroxyl methacrylate and 58 parts of Emulken 109P (polyethylene oxide monolauryl ether, manufactured by Kao) were added.
1 part of hydroquinone, 3 parts of N,N-dimethylbenzylamine and 330 parts of xylene, and further heated to 135°C.
The reaction was carried out for 130 minutes.

The resulting resin had a solid concentration of 60% and an average molecular weight of 40.40.
0 and the resin solid content acid value was 40, and it was confirmed by IR spectrum measurement that it had a double bond capable of radical polymerization.

) Example 3 Trimellitic anhydride 192 was added to a 2e capacity four-bottle flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer.
1 part, 224 parts of Plaxel FM-1 (1.1 mol adduct of hydroquine methacrylate and ε-caprolactone, manufactured by Daicel Chemical), 100 parts of nclohexanone, and 0.1 part of hydroquinone, and then heated to 150 parts under a nitrogen stream.
The reaction was carried out for 05 hours at 'C.

Further, 740 parts of Bunacol 992 (polytetramethylene glycol dicrycidyl ether, manufactured by Nagase Chemical Industries, Ltd.), 400 parts of cyclohexanone, and 0.1 part of hydroquinone were charged, and a reaction was carried out at 150° C. for 60 minutes.

The resulting resin had a solid concentration of 70% and an average molecular weight of 2°400.
The resin solid content had an acid value of 48, and it was confirmed by IR spectrum measurement that it had a double bond capable of polymerization.

(Manufacture of crosslinked resin particles (1)) Production example 1 Dispersion step: 140 parts of the 100% neutralized product of 7-methyl ethanolamine of the resin of Reference example 1, 20 parts of methyl methacrylate, and 2 parts of vinylhense are mixed to become uniform. Stir until Additionally, 450 parts of deionized water and 5 parts of n-propyl alcohol
0 parts was added, and emulsification was performed at 70°C for 130 minutes using a homogenizer.

Crosslinking process.

The obtained emul/con was transferred to a 2E four-bottle flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, and separately prepared radical polymerization initiators A, CJ, A,
(4,4'-7zobis-4-cyanovalerinoquacid, manufactured by Otsuka Chemical) 1 part dimethylethanolamine 100
After adding 100 parts of an aqueous solution of the neutralized product, the
A crosslinking reaction by radical polymerization was carried out at 5° C. for 2 hours.

The average particle size of the resin emulsion prepared in the above steps was 110 parts m (observed by electron microscopy).

Aqueous solvent removal step: While stirring the obtained emulsion, a 1% aqueous calcium chloride solution was gradually added to salt out the resin particles, which were precipitated as fine aggregates (particle size of 0.1 to several my). Therefore, filtration, washing and vacuum drying (45℃, 0.5To
rr) to obtain dry particles.

Production Example 2 Dispersion Step - 100% dimethyl ethyl/-ruamino of 111+1 resin
140 parts of neutralized product, 20 parts of styrene monomer 1,6-
Three parts of hexanediol methacrylate were mixed and stirred until homogeneous. Additionally, 450 parts of deionized water and n-
Add 50 parts of propyl alcohol and use a homogenizer to
Emulsification operation was performed at 0°C for 130 minutes.

Crosslinking process.

The obtained emulsion was transferred to a 2 g four-bottle flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and radical polymerization initiators A, C, V, and A prepared separately were added.
(4,4'-azobis-4-na/valerinoquacid, manufactured by Otsuka Chemical) 1 part dimethylethanolamine 10
A crosslinking reaction by radical polymerization was carried out at 85° C. for 2 hours under a nitrogen stream to which 100 parts of an aqueous solution of 0% +Del was added. The average particle diameter of the resin emulsion prepared in the above steps was 124 run (observed using an electron microscope).

Aqueous solvent removal process When the obtained emulsion was salted out by gradually adding a 1% aqueous calcium chloride solution while stirring, the resin particles became fine aggregates (particle size of 0.1 to several square meters). Due to precipitation, filtration, washing and vacuum drying (45°C, 0.5 Torr) were performed.
Dry particles were obtained by carrying out step r).

Production Example 3 Dispersion Step: 140 parts of 100% neutralized dimethylethanolamine of the resin of Reference Example 1, 100 parts of a 20% xylene solution of polymethyl methacrylate (estimated number average molecular weight approximately 300,000), and 3 parts of neopentyl glycol dimethacrylate. mix,
Stir until homogeneous. Further, 450 parts of ionized water and 50 parts of n-propyl alcohol were added, and emulsification was carried out using a homogenizer for 130 minutes at 70'C.

Crosslinking step: The obtained emulsion was transferred to a 2E four-bottle flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and separately prepared radical polymerization initiators A, CV, A,
(4,4"-azobis-4-cyanovalerisoquinone, manufactured by Otsuka Chemical) 1 part dimethylethanolamine 100
After adding 100 parts of an aqueous solution of the neutralized product, the
A crosslinking reaction by radical polymerization was carried out at 5° C. for 2 hours.

The average particle diameter of the resin emulsion prepared in the above steps was 145 nm (ii) by electron microscopy observation.

Aqueous solvent removal step: While stirring the obtained emulsion, 1% aqueous calcium chloride solution was gradually added to salt out the resin particles, which precipitated out as fine aggregates (particle size 0.1 to several j+x). Therefore, filtration, washing and vacuum drying (45℃ 1Q, 5T
orr) to obtain dry particles.

Production Example 4 Dispersion Process 120 parts of a 100% dimethylethanolamine neutralized product of the resin of Reference Example t, 60 parts of a 50% butyl acetate solution of YD-014' (bisphenol type Evokin resin, manufactured by Tobu Kagaku), and ethylene glyfur dimethacrylate. 05 parts were mixed and stirred until homogeneous. Plus deionized water, 45
0 parts and 50 parts of n-propyl alcohol were added, and emulsification was performed using a homogenizer for 130 minutes at 70'C.

Crosslinking process The obtained emulsion was transferred to a 2Q four-bottle flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, and thermometer, and separately prepared radical polymerization initiators A, C, V, and A were added.
, (4,4'-Azobis-4-ananovalerinokuacinodo, Oganka Kagaku H) After adding 100 parts of an aqueous solution of 1 part of 100% neutralized dimethylethanolamine, 2 A crosslinking reaction was carried out by time radical polymerization. The average particle diameter of the resin emul/con prepared in the above steps was 131 nm (observed using an electron microscope).

Aqueous solvent removal process When the obtained emulsion was salted out by gradually adding a 1% aqueous calcium chloride solution while stirring, the resin particles precipitated as fine aggregates (particle size 01 to several U), so they were filtered. , washing and vacuum drying (45°C, Q5 Torr)
to obtain dry particles.

100% neutralized dimethylethanolamine of the resin from Example 2 OL 15 parts of styrene monomer, 15 parts of ethyl methacrylate, and 10 parts of propylene glycol noacrylate were mixed and stirred until homogeneous. . Additionally, 430 parts of deionized water and 50 parts of isopropyl alcohol
and emulsification was performed using a homogenizer for 130 minutes at 70'C.

Crosslinking step: The obtained emulsion was transferred to a 2Q four-bottle flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and separately prepared radical polymerization initiators A, CJ, A,
(4,4'-Azobis-4-thia/valylic acid, manufactured by Daichu Kagaku) 1 part dimethylethanolamine 100
After adding 100 parts of an aqueous solution of the neutralized product, the
A crosslinking reaction by radical polymerization was carried out at 5° C. for 2 hours.

The average particle diameter of the resin emulsion prepared in the above steps was 254 nm (observed using an electron microscope).

Aqueous solvent removal step - While stirring the obtained emulsion, a 1% aqueous calcium chloride solution was gradually added to salt out the resin particles, which precipitated out as fine aggregates (particle size of 0.1 part/several mm). , filtration, washing and vacuum drying (45°C, Q, 5To
rr) to obtain dry particles.

Manufacturing example 6 Dispersion process.

Reference h+2 resin dimethylethanolamine 100%
120 parts of neutralized product, polystyrene (estimated number average molecular weight approximately 3
150 parts of a 20% quintessence solution (100,000) and 0.1 part of trivinylbenzene were mixed and stirred until homogeneous. Further, 450 parts of deionized water and 50 parts of isopropyl alcohol were added, and emulsification was performed at 70°C for 130 minutes using a homogenizer.

Crosslinking step: The obtained emulsion was transferred to a four-bottle flask with a 2ρ container equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and separately prepared radical polymerization initiators A, C, and VJ were added.
(4+4'-7 sobisu-4-one anovalerinokannod, manufactured by Daika Kagaku) 1 part dimethylethanolamine 100
After adding 100 parts of an aqueous solution of the neutralized product, the
A crosslinking reaction by radical polymerization was carried out at 5° C. for 2 hours.

The average particle diameter of the resin emulsion prepared in the above steps was 190 nm (observed using an i-son microscope).

Aqueous solvent removal step: While stirring the obtained emulsion, 1% aqueous carunium chloride solution was gradually added for salting out, and the resin particles precipitated as fine aggregates (particle size 01 to several xx). Filtration, washing and vacuum drying (45°C, 0.5 Torr)
Dry particles were obtained by carrying out step r).

Production Example 7 Dispersion Process 140 parts of 100% neutralized product of 7-methylated ethanolamine of the resin of Reference Example 3, Tyamide-PAE (boamide resin,
(manufactured by Teiselhüls) 7 Kurohe Beef Non 30% Solution 6
7 parts of trimethylolpropane triacrylate and 1 part of V-65 (2,2 asobis-(2,4-7 methylhaleronitrile), manufactured by Aiko Pure Chemical Industries, Ltd.) were mixed and stirred until uniform. Further, an emulsification operation was performed for 130 minutes at 70'C with 600 parts of deionized water.

[Kanneyeng] The obtained emul/container was transferred to a 2 g four-bottle flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, and a crosslinking reaction by radical polymerization was carried out at 75°C under a nitrogen stream for 1 hour. I did it. The average particle diameter of the resin emulsion prepared in the above steps was 70 parts m (ii) by electron microscopy observation.

Aqueous solvent removal step - While stirring the obtained emulsion, a 1% aqueous calcium chloride solution was gradually added to salt out the resin particles, which turned into fine aggregates (particle size of 0.1 to several yrx). Since the precipitates precipitated during treatment, washing and vacuum drying (45℃, 0.5T)
orr) to obtain dry particles.

Production example 8 Dispersion step AC-PTGlooO (polytetramethylene gnocolon acrylate molecule 1 approximately 1,200, manufactured by Hodogaya Chemical)
60 parts, 2 parts of N,N'-7,1 methyl acrylate, 1 part of acrylonitrile, 2 parts of ethylene chloride/col/IJ rate 5L2-hydroquine ethyl methacrylate, 30 parts of isoflovir methacrylate, and V
-60 (abbisinobutyronitrile, manufactured by Wako Pure Chemical Industries) 1
The parts were mixed and stirred until homogeneous. Furthermore, 400 parts of a 1% aqueous solution of sodium lauryl sulfate was added, and emulsification was performed using a homogenizer for 130 minutes at 70'C.

Crosslinking process The obtained emulsion was transferred to a 2A four-bottle flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and a crosslinking reaction by Rancal polymerization was carried out at 75° C. under a nitrogen stream for 1 hour. The average particle diameter of the resin emulsion prepared in the above steps was 120 nm (observed using an electron microscope).

Aqueous solvent removal step The obtained emulsion was spray-dried to obtain dry particles.

Production Example 9 Dispersion Step HYCAR, VTBNX, BOOX23 (butashiacrylonitrile copolymer with both terminals hynylated, molecule 1
3.500, manufactured by Ube Industries), 1 part of novinylbencef, 2 parts of N,N-dimethylaminoethquin ethyl acrylate, and 10 parts of a 100% neutralized product of the resin of Reference Example 1 with dimethylethanolamine, Stir until homogeneous.

Further, 900 parts of deionized water and 90 parts of isopropyl alcohol were added, and emulsification was performed using a homogenizer at 70° C. for 30 minutes.

Crosslinking step: The obtained emulsion was transferred to a four-bottle flask with a 2ρ container equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, and a thermometer, and the separately prepared radical polymerization initiators A, CJ, A, (
4,4°-azobis-4-cyanovalerinoquannode,
1 part dimethylethanolamine 100%
After adding 100 parts of an aqueous solution of the neutralized product, 85 parts of the aqueous solution was added under a nitrogen stream.
A crosslinking reaction by Rancal polymerization was carried out at ℃ for 2 hours. The average particle diameter of the resin emulsion prepared in the above steps was 10100n (as determined by electron microscopy).

Aqueous solvent removal step The obtained emulsion was freeze-dried to obtain dry particles.

Comparative Production Example 1 Dispersion Step: 140 parts of a 100% dimethylethanolamine neutralized product of the resin of Glue Example 1 and 20 parts of methyl methacrylate were mixed and stirred until uniform. Further, 450 parts of deionized water and 50 parts of n-propyl alcohol were added, and emulsification was performed using a homogenizer at 70°C for 130 minutes.

Crosslinking step The obtained emulsion was transferred to a 2A four-bottle flask equipped with a stirrer, reflux condenser, nitrogen inlet tube and thermometer, and separately prepared radical polymerization initiators A, C, V, A,
(4, 4-7 Sohisu 4-/7 Novareli, Quan, Do,
(manufactured by Daichu Kagaku) 1 part methylethanolamine 100%
After adding 1 IJI 00 parts of neutralized water, 8 parts of water was added under a nitrogen stream.
A crosslinking reaction was carried out by polymerization/cal polymerization at 5° C. for 2 hours.

The average particle diameter of the resin emul/gin prepared in the above steps was l 00 nm (observed using an electron microscope).

Aqueous solvent removal step: While stirring the obtained emulsion, a 1% aqueous calcium chloride solution was gradually added to salt out the resin particles, which precipitated out as fine aggregates (particle size of 0.1 to several nanometers). , filtration, washing and vacuum drying (45°C 10,5 Tor
Dry particles were obtained by carrying out step r).

(Preparation of photosensitive resin composition) Example 1 To 60 parts of the dry particles produced in Production Example 1, 58 parts of NN-dimethylaminopropyl methacrylamide, 55 parts of polyethylene glycol nonylphenyl ether, and 55 parts of phenoxy/ethoquinoethanol were added. parts, dipropylene glycol monomethyl monoacrylate 11 parts, nonaethylene glyfur diacrylate 5 parts, trimethylolpropane trimethacrylate 5 parts, 2,2-cymethoxy/-2-
1.8 parts of phenylacetophenone, and 2.6 parts of phenylacetophenone
04 parts of Fuchirup P Cresol was added. The resulting mixture was thoroughly mixed using a two-screw kettle. The photopolymerized resin composition thus obtained was extruded onto an iron plate using an eta extruder equipped with a T-die to obtain a plate having a photosensitive resin layer with a thickness of about 0.4011 mm. Next, a negative film having an appropriate image is uniformly brought into contact with the surface of the photosensitive resin layer of the photosensitive resin plate, and after being irradiated with a 350W chemical lamp for 1 hour, the negative film is developed by developing with water at 40'C. We were able to create a resin white board that was faithful to the above.

Using this printing plate, printing conditions were 600 on a flexo printing machine.
Printing was carried out using an aqueous flexo ink at 1 ft/min. After printing 150,000 sheets, no changes were observed on the surface of the printing plate.

Examples 2 to 7 Photosensitive resin compositions were prepared in the same manner as in Example 1, except that 60 parts of the dry particles produced in Production Examples 2 to 7 were used instead of the dry particles in Production Example 1, This was coated to form a photosensitive resin layer having a thickness of about 0.40xx, thereby obtaining a photosensitive resin plate. Using these printing plates, printing was carried out using water-based flexographic ink on a flexographic printing machine under printing conditions of 600 feet/min. After printing 150,000 sheets,
No change was observed on the surface of the printing plate.

Examples 8 and 9 For 60 parts of each dry particle produced in Production Examples 8 and 9,
5.8 parts of methacrylic acid, 5.5 parts of polyethylene glycol nonylphenyl ether, 5.5 parts of phenoxyethoxyethanol, 11 parts of dipropylene glycol monomethyl monoacrylate, 5 parts of nonaethylene glyfur diacrylate, 5 parts of trimethylolpropane trimethacrylate. , 1.8 parts of 2,2-diftquine-2-phenylacetophenone, and 04 parts of 2,6-sheet t-butyl-p-cresol were added. The resulting mixture was thoroughly mixed using a pressurized twin-screw kneader. The photopolymerized resin composition thus obtained was extruded onto an iron plate using a Nida extruder equipped with a T-pull to obtain a plate having a photosensitive resin layer with a thickness of about 0.40U. Next, a negative film having a suitable image is uniformly brought into contact with the surface of the photosensitive resin layer of the photosensitive resin plate, and after being irradiated with a 350W chemical lamp for 1 hour, the film is developed with water at 40°C to form a negative film. I was able to create a faithful l-fat convex plate.

Using these printing plates, printing conditions 6 were applied to a flexo printing machine.
Printing was carried out using a water-based flexographic ink at 0.00 feet/min. l 50. After printing OO0 sheets, no change was observed on the surface of the printing plate.

K Umemasuto l For 60 parts of each dry particle produced in Production Example 1, N, N
5.8 parts of polyethylene glycol/nylphenyl ether
5 parts, phenol/ethquin ethanol 5.5 L/propylene glycol monomethyl monoacrylate 11.0
) (50 parts of X-620 (manufactured by Kuchmoto Kayaku), 50 parts of diethylene glycol/methacrylate, 18 parts of 2,2>methoquino-2phenylacetophene, and 2.6 parts of 04 parts of Fresol was removed.The resulting mixture was thoroughly mixed by pressurizing twin screws overnight.This composition was extruded into a sorted form, and at the same time, it was placed on a support at 80°C via a spacer under low pressure. A photosensitive resin plate with a thickness of 0.4xx was obtained using a press.

These printing plates were used to print with newsprint flexo inks using a flexo printing machine at a printing speed of 120 feet per minute. Printing was smooth with some mottling.

Examples 11 to 16 Photosensitive resin compositions were prepared in the same manner as in Example 10, except that 60 parts of the dry particles prepared in Production Examples 2 to 7 were used instead of the dry particles in Production Example 1. Then, this was coated on the substrate to form a photosensitive resin layer with a thickness of about 0401 mm,
A photosensitive resin plate was obtained.

When printing was carried out in the same manner as in Example 10 using these resin plates, clear images were obtained.

Example 17 and Otsura 8 For 60 parts of each dry particle prepared in Production Examples 8 and 9,
58 parts of methacrylic acid, 5.5 parts of polyethylene gutucol/nylphenyl ether, 55 parts of fenoquinethoquinoethanol, 11.0 parts of propylene glycol monomethyl monoacrylate, HX-620 (manufactured by Nippon Kayaku) 5
0 parts, 50 parts of diethylene glycol dimethacrylate,
2゜2-/Methoquino-2-phenylacetofu 218
and 0.4 parts of 2,6-sheet t-butyl-p-cresol were added. The resulting mixture was thoroughly mixed using a pressurized twin-screw kneader. This composition was extruded into a sorted form, and at the same time, a 0.4xx thick photosensitive resin plate was obtained on a support using a low pressure press at 80'C via a spacer.

When these resin plates were used for printing in the same manner as in Example 10, clear images were obtained.

(Water developability and storage stability test) Photosensitive resin plate produced in Example 1 and Production Example 1
A sample having a thickness of about 0.403 mm produced by the same method as in Example 1 using the dry particles of Comparative Production Example 1 instead of the dry particles of
! A plate having a photosensitive resin layer of 2 (comparative example 1)
Two sheets of each were used in the test. first,
After each plate was exposed and cured in the same manner as in Example 1, the time required for water development at 40'C (
Water development time) was measured. Further, each of the remaining plates was left in a dark place at 40° C. for one week, and then the time required for water development was measured in the same manner. The experimental results for both are shown below.

From these results, the photosensitive resin composition of the present invention has excellent water developability compared to conventional ones, and is easily water developable without curing even if left in a dark place for a long time. and exhibits excellent storage stability.

Claims (1)

[Claims] (1) (I) (i) A resin with a glass transition temperature (Tg) of 0°C or less, (ii) A resin whose Tg is 20°C or more higher than resin (i), or a monomer that provides it, (iii) Polymer Crosslinked resin particles obtained by subjecting each blend of a functional vinyl compound and (iv) a polymerization initiator to a post-emulsification method, (II) a photopolymerizable unsaturated monomer, and (III) photopolymerization initiation A photosensitive resin composition containing a photosensitive agent.